Desulfurization and novel compositions for same

ABSTRACT

A composition comprising manganese oxide and a promoter, wherein at least a portion of the promoter is present as a reduced valence promoter and methods of preparing such composition are disclosed. The thus-obtained composition is employed in a desulfurization zone to remove sulfur from a hydrocarbon stream.

FIELD OF THE INVENTION

[0001] This invention relates to the removal of sulfur from hydrocarbonstreams. In another aspect, this invention relates to compositionssuitable for use in the desulfurization of fluid streams of crackedgasolines and diesel fuels. A further aspect of this invention relatesto processes for the production of compositions for use in the removalof sulfur bodies from fluid streams of cracked gasolines and dieselfuels.

BACKGROUND OF THE INVENTION

[0002] The need for cleaner burning fuels has resulted in a continuingworld-wide effort to reduce sulfur levels in hydrocarbon streams such asgasoline and diesel fuels. The reduction of sulfur in such hydrocarbonstreams is considered to be a means for improving air quality because ofthe negative impact the sulfur has on performance of sulfur sensitiveitems such as automotive catalytic converters. The presence of oxides ofsulfur in automotive engine exhaust inhibits and may irreversibly poisonnoble metal catalysts in the converter. Emissions from an inefficient orpoisoned converter contain levels of non-combusted, non-methanehydrocarbons, oxides of nitrogen, and carbon monoxide. Such emissionsare catalyzed by sunlight to form ground level ozone, more commonlyreferred to as smog.

[0003] Thermally processed gasolines such as, for example, thermallycracked gasoline, visbreaker gasoline, coker gasoline and catalyticallycracked gasoline (hereinafter collectively referred to as “crackedgasoline”) contain, in part, olefins, aromatics, sulfur, and sulfurcontaining compounds. Since most gasolines, such as, automobilegasolines, racing gasolines, aviation gasolines, boat gasolines, and thelike contain a blend of, at least in part, cracked gasoline, reductionof sulfur in cracked gasoline will inherently serve to reduce the sulfurlevels in most gasolines, such as, for example, automobile gasolines,racing gasolines, aviation gasolines, boat gasolines, and the like.

[0004] The public discussion about gasoline sulfur has not centered onwhether or not sulfur levels should be reduced. A consensus has emergedthat lower sulfur gasoline reduces automotive emissions and improves airquality. Thus, the rules to date have focused on the required level ofreduction, the geographical areas in need of lower sulfur gasoline, andthe time frame for implementation.

[0005] As the concern over the impact of automotive air pollutioncontinues, it is clear that further effort to reduce the sulfur level inautomotive fuels will be required. While the current gasoline productscontain about 330 parts per million (ppm) sulfur, the US EnvironmentalProtection Agency recently issued regulations requiring the averagesulfur content in gasoline to be less than 30 ppm average with an 80 ppmcap. By 2006, the standards will effectively require every blend ofgasoline sold in the United States to meet the 30 ppm level.

[0006] In addition to the need to be able to produce low sulfur contentautomotive fuels, there is also a need for a process which will have aminimal effect on the olefin content of such fuels so as to maintain theoctane number (both research and motor octane number). Such a processwould be desirable since saturation of olefins greatly affects theoctane number. Such adverse effect on the olefin content is generallydue to the severe conditions normally employed, such as duringhydrodesulfurization, to remove thiophenic compounds (such as, forexample, thiophenes, benzothiophenes, alkyl thiophenes,alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which aresome of the most difficult sulfur containing compounds to remove fromcracked gasoline. In addition, there is a need to avoid a system whereinthe conditions are such that the aromatic content of the crackedgasoline is lost through saturation. Thus, there is a need for a processwhich achieves desulfurization and maintains the octane number.

[0007] In addition to the need for removal of sulfur from crackedgasolines, there is a need for the petroleum industry to reduce thesulfur content in diesel fuels. In removing sulfur from diesel fuels byhydrodesulfurization, the cetane is improved but there is a large costin hydrogen consumption. Such hydrogen is consumed by bothhydrodesulfurization and aromatic hydrogenation reaction.

[0008] Thus, there is a need for a desulfurization process without asignificant consumption of hydrogen so as to provide a more economicalprocess for the treatment of cracked gasolines and diesel fuels.

[0009] As a result of the lack of success in providing a successful andeconomically feasible process for the reduction of sulfur levels incracked gasolines and diesel fuels, it is apparent that there is a needfor a better process for the desulfurization of such hydrocarbon streamswhich has minimal effect on octane levels while achieving high levels ofsulfur removal.

[0010] Traditionally, compositions used in processes for the removal ofsulfur from hydrocarbon streams have been agglomerates used in fixed bedapplications. Because of the various process advantages of fluidizedbeds, hydrocarbon streams are sometimes processed in fluidized bedreactors. Fluidized bed reactors have advantages over fixed bedreactors, such as, for example, better heat transfer and better pressuredrop. Fluidized bed reactors generally use reactants that areparticulate. The size of these particulates is generally in the range offrom about 1 micron to about 1000 microns. However, the reactants usedgenerally do not have sufficient attrition resistance for allapplications. Consequently, finding a composition with sufficientattrition resistance that removes sulfur from these hydrocarbon streamsand that can be used in fluidized, transport, moving, or fixed bedreactors is desirable and would be a significant contribution to the artand to the economy.

SUMMARY OF THE INVENTION

[0011] It is thus an object of the present invention to provide novelcompositions that can be used for the removal of sulfur from hydrocarbonstreams.

[0012] Another object of the present invention is to provide processesfor the production of novel compositions which are usable in thedesulfurization of hydrocarbon streams.

[0013] Another object of the present invention is to provide a processfor the removal of sulfur from hydrocarbon streams which minimizes theconsumption of hydrogen and the saturation of olefins and aromaticscontained in such streams.

[0014] A still further object of the present invention is to provide adesulfurized cracked gasoline that contains less than about 100 ppm,preferably less than 50 ppm, of sulfur based on the weight of thedesulfurized cracked gasoline, and which contains essentially the sameamount of olefins and aromatics as are in the cracked gasoline fromwhich such desulfurized cracked gasoline was made.

[0015] This invention includes a novel composition suitable for use indesulfurizing hydrocarbons. The novel composition comprises:

[0016] a) manganese oxide; and

[0017] b) a promoter wherein at least a portion of the promoter ispresent as a reduced valence promoter.

[0018] The invention further includes another novel composition suitablefor use in desulfurizing hydrocarbons. The novel composition comprises:a) manganese oxide; b) a silicon-containing material; c) analuminum-containing material selected from the group consisting ofalumina, aluminate and combinations thereof; and d) a promoter whereinat least a portion of the promoter is present as a reduced valencepromoter.

[0019] This invention also includes a novel process for the productionof the inventive composition comprising:

[0020] a) admixing: 1) a liquid, 2) manganese oxide, 3) asilicon-containing material, 4) alumina, and 5) a promoter so as to forma mixture thereof;

[0021] b) drying the mixture so as to form a dried mixture;

[0022] c) calcining the dried mixture so as to form a calcined mixture;

[0023] d) reducing the calcined mixture with a suitable reducing agentunder W suitable conditions to produce a composition having a reducedvalence promoter content therein, and

[0024] e) recovering the composition.

[0025] This invention further includes another novel process for theproduction of the inventive composition comprising:

[0026] a) admixing: 1) a liquid, 2) manganese oxide, 3) asilicon-containing material, and 4) alumina so as to form a mixturethereof;

[0027] b) drying the mixture so as to form a dried mixture;

[0028] c) calcining the dried mixture so as to form a calcined mixture;

[0029] d) incorporating a promoter onto or into the calcined mixture soas to form a promoted mixture;

[0030] e) drying the promoted mixture so as to form a dried promotedmixture;

[0031] f) calcining the dried promoted mixture so as to form a calcinedpromoted mixture;

[0032] g) reducing the calcined promoted mixture with a suitablereducing agent under suitable conditions to produce a composition havinga reduced valence promoter content therein; and

[0033] h) recovering the composition.

[0034] This invention still further includes a process for the removalof sulfur from a hydrocarbon stream comprising:

[0035] a) contacting the hydrocarbon stream with a compositioncomprising manganese oxide, and a promoter wherein at least a portion ofthe promoter is present as a reduced valence promoter in an amount whichwill effect the removal of sulfur from the hydrocarbon stream in adesulfurization zone under conditions such that there is formed adesulfurized hydrocarbon stream and a sulfurized composition;

[0036] b) separating the desulfurized hydrocarbon stream from thesulfurized composition thereby forming a separated desulfurizedhydrocarbon stream and a separated sulfurized composition;

[0037] c) regenerating at least a portion of the separated sulfurizedcomposition in a regeneration zone so as to remove at least a portion ofthe sulfur contained therein and/or thereon thereby forming aregenerated composition;

[0038] d) reducing the regenerated composition in an activation zone soas to provide a reduced composition having a reduced valence promotercontent therein which will effect the removal of sulfur from ahydrocarbon stream when contacted with same; and thereafter

[0039] e) returning at least a portion of the reduced composition to thedesulfurization zone.

[0040] In step (a), the composition can also comprise, consist of, orconsist essentially of manganese oxide, a silicon-containing material,an aluminum-containing material selected from the group consisting ofalumina, aluminate and combinations thereof, and a promoter wherein atleast a portion of the promoter is present as a reduced valence promoterin an amount which will effect the removal of sulfur from thehydrocarbon stream in a desulfurization zone under conditions such thatthere is formed a desulfurized hydrocarbon stream and a sulfurizedcomposition.

[0041] Other aspects, objectives, and advantages of the presentinvention will be apparent from the detailed description of theinvention and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

[0042] The term “gasoline” denotes a mixture of hydrocarbons boiling inthe range of from about 100° F. to about 500° F., or any fractionthereof. Examples of suitable gasoline include, but are not limited to,hydrocarbon streams in refineries such as naphtha, straight run naphtha,coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate,isomerate, reformate, and the like and combinations thereof.

[0043] The term “cracked gasoline” denotes a mixture of hydrocarbonsboiling in the range of from about 100° F. to about 500° F., or anyfraction thereof, that are products from either thermal or catalyticprocesses that crack larger hydrocarbon molecules into smallermolecules. Examples of suitable thermal processes include, but are notlimited to, coking, thermal cracking, visbreaking, and the like andcombinations thereof. Examples of suitable catalytic cracking processesinclude, but are not limited to, fluid catalytic cracking, heavy oilcracking, and the like and combinations thereof. Thus, examples ofsuitable cracked gasoline include, but are not limited to, cokergasoline, thermally cracked gasoline, visbreaker gasoline, fluidcatalytically cracked gasoline, heavy oil cracked gasoline, and the likeand combinations thereof. In some instances, the cracked gasoline may befractionated and/or hydrotreated prior to desulfurization when used as ahydrocarbon stream in the process of the present invention.

[0044] The term “diesel fuel” denotes a mixture of hydrocarbons boilingin the range of from about 300° F. to about 750° F., or any fractionthereof. Examples of suitable diesel fuels include, but are not limitedto, light cycle oil, kerosene, jet fuel, straight-run diesel,hydrotreated diesel, and the like and combinations thereof.

[0045] The term “sulfur” denotes sulfur in any form such as elementalsulfur or a sulfur compound normally present in a hydrocarbon-containingfluid such as cracked gasoline or diesel fuel. Examples of sulfur whichcan be present during a process of the present invention usuallycontained in a hydrocarbon stream, include, but are not limited to,hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS₂),mercaptans (RSH), organic sulfides (R—S—R), organic disulfides(R—S—S—R), thiophenes, substituted thiophenes, organic trisulfides,organic tetrasulfides, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes, and the like and combinationsthereof as well as the heavier molecular weights of same which arenormally present in a diesel fuel of the types contemplated for use in aprocess of the present invention, wherein each R can be an alkyl orcycloalkyl or aryl group containing one carbon atom to ten carbon atoms.

[0046] The term “fluid” denotes gas, liquid, vapor, and combinationsthereof.

[0047] The term “gaseous” denotes that state in which thehydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel,is primarily in a gas or vapor phase.

[0048] The inventive composition comprises manganese oxide and apromoter.

[0049] The inventive composition can also comprise, consist of, orconsist essentially of manganese oxide, an aluminum-containing materialselected from the group consisting of alumina, aluminate, andcombinations thereof, a silicon-containing material, and a promoter.

[0050] The term “manganese oxide,” as used herein, denotes any oxide ofmanganese, including, but not limited to, MnO, Mn₃O₄, Mn₂O₃, MnO₂, MnO₃,and Mn₂O₇.

[0051] The silicon-containing material used in the preparation of, andpresent in the inventive compositions may be either in the form ofsilica or in the form of one or more silicon-containing materials.

[0052] Any suitable source of silicon may be employed in the compositionsuch as, for example, diatomite, expanded perlite, silicalite, silicacolloid, flame-hydrolized silica, silica gel, precipitated silica, andthe like, and combinations thereof. In addition, silicon compounds thatare convertible to silica such as silicic acid, ammonium silicate, andthe like, and combinations thereof can also be employed.

[0053] More preferably the silicon-containing material is in the form ofexpanded perlite. The term “perlite” as used herein is the petrographicterm for a siliceous volcanic rock, which naturally occurs in certainregions throughout the world. The distinguishing feature, which sets itapart from other volcanic minerals, is its ability to expand four totwenty times its original volume when heated to certain temperatures.When heated above 1600° F., crushed perlite expands due to the presenceof combined water with the crude perlite rock. The combined watervaporizes during the heating process and creates countless tiny bubblesin the heat softened glassy particles. The diminutive glass sealedbubbles account for its light weight. Expanded perlite can bemanufactured to weigh as little as 2.5 lbs per cubic foot.

[0054] The typical elemental analysis of expanded perlite is: silicon33.8%, aluminum 7%, potassium 3.5%, sodium 3.4%, calcium 0.6%, magnesium0.2%, iron 0.6%, trace elements 0.2%, oxygen (by difference) 47.5%, andbound water 3%.

[0055] Typical physical properties of expanded perlite are: softeningpoint 1600-2000° F., fusion point 2300-2450° F., pH 6.6-6.8, andspecific gravity 2.2-2.4.

[0056] The term “particulate expanded perlite” or “milled perlite” asused herein denotes that form of expanded perlite which has beensubjected to crushing so as to form a particulate mass wherein theparticle size of such mass is comprised of at least 97% of particleshaving a size of less than 2 microns.

[0057] The term “milled expanded perlite” is intended to mean theproduct resulting from subjecting expanded perlite particles to millingor crushing.

[0058] The inventive composition contains an aluminum-containingmaterial selected from the group consisting of alumina, aluminate, andcombinations thereof. Alumina can be used to produce the composition.The alumina employed in the preparation of the composition can be anysuitable commercially available alumina material such as, for example,colloidal alumina solutions, hydrated aluminas, peptized aluminas, and,generally, those alumina compounds produced by the dehydration ofalumina hydrates. The preferred alumina is hydrated alumina such as, forexample, bohemite or pseudobohemite for best activity and sulfurremoval. When the composition is exposed to high temperatures (e.g.,during calcinations) at least a portion, preferably a substantialportion of the alumina can be converted to an aluminate.

[0059] The term “promoter” denotes any component, which when added tothe composition of the present invention, helps promote thedesulfurization of hydrocarbon streams. Such promoters can be at leastone metal, metal oxide, precursor for the metal oxide, solid solution ofmore than one metal, or alloy of more than one metal wherein the metalcomponent is selected from the group consisting of nickel, cobalt, iron,manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony,vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, andcombinations of any two or more thereof.

[0060] Some examples of promoter metal containing compounds includemetal acetates, metal carbonates, metal nitrates, metal sulfates, metalthiocyanates, and the like and combinations thereof. Preferably, themetal of the promoter is selected from the group consisting of nickel,cobalt, nickel-zinc, and combinations of any two or more thereof.

[0061] The inventive composition having a reduced valence promotercontent is a composition that has the ability to react chemically and/orphysically with sulfur. It is also preferable that the inventivecomposition removes diolefins and other gum forming compounds fromcracked gasoline.

[0062] The term “metal” denotes metal in any form such as elementalmetal or a metal-containing compound.

[0063] The term “metal oxide” denotes metal oxide in any form such as ametal oxide or a metal oxide precursor.

[0064] During the preparation of a composition of the present invention,the promoter selected from the group consisting of metals, metal oxides,and the like and combinations thereof may initially be in the form of ametal-containing compound and/or a metal oxide precursor. It should beunderstood that when the promoter is initially a metal-containingcompound and/or a metal oxide precursor, a portion of, or all of, suchcompound and/or precursor may be converted to the corresponding metal ormetal oxide of such compound and/or precursor during the inventiveprocess disclosed herein.

[0065] Typically, the common oxidation state of the promoter is combinedwith the manganese oxide portion of the inventive composition. Thenumber of oxygen atoms associated with the promoter must be reduced toform a reduced valence promoter. Consequently, at least a portion of thepromoter present in the inventive composition must be present as areduced valence promoter. While not wishing to be bound by theory, it isbelieved that the reduced valence promoter can chemisorb, cleave, orremove sulfur. Thus, either the number of oxygen atoms associated withthe promoter is reduced or the oxidation state of the promoter is azero-valent metal. For example, if nickel is the promoter metal, nickeloxide (NiO) can be used and the reduced valence nickel (promoter metal)can be either nickel metal (Ni⁰) or a non-stoichiometric nickel oxidehaving a formula of NiO_((1-x)) wherein 0<x<1. If tungsten is thepromoter, tungsten oxide (WO₃) can be used and the reduced valencetungsten (promoter metal) can be either tungsten oxide (WO₂), tungstenmetal (W⁰), or a non-stoichiometric tungsten oxide having a formula ofWO_((3-y)) wherein 0<y<3.

[0066] Preferably, the promoter is present in an amount which willeffect the removal of sulfur from the hydrocarbon stream when contactedwith the inventive composition under desulfurization conditions. Of thetotal quantity of the promoter present in the inventive composition, itis preferred for at least about 10 weight percent of the promoter to bepresent in the form of a reduced valence promoter, more preferably atleast about 40 weight percent of the promoter is a reduced valencepromoter, and most preferably at least 80 weight percent of the promoteris a reduced valence promoter for best activity in sulfur removal. Thereduced valence promoter will generally be present in the inventivecomposition in an amount in the range of from about 1 to about 60 weightpercent reduced valence promoter based on the total weight of theinventive composition, preferably in an amount in the range of fromabout 5 to about 40 weight percent reduced valence promoter, and mostpreferably in an amount in the range of from 8 to 20 weight percentreduced valence promoter for best activity in sulfur removal. When thepromoter comprises a bimetallic promoter, the bimetallic promoter shouldcomprise a ratio of the two metals forming such bimetallic promoter inthe range of from about 20:1 to about 1:20.

[0067] The manganese oxide will preferably be present in the inventivecomposition in an amount in the range of from about 10 to about 90weight percent manganese oxide based on the total weight of theinventive composition, more preferably in an amount in the range of fromabout 40 to about 80 weight percent manganese oxide, and most preferablyin an amount in the range of from about 50 to about 70 weight percentmanganese oxide.

[0068] The manganese oxide used in the preparation of a composition ofthe present invention can either be in the form of manganese oxide or inthe form of one or more manganese compounds that are convertible tomanganese oxide under the conditions of preparation described herein.Examples of suitable manganese compounds include, but are not limitedto, manganese sulfide, manganese sulfate, manganese hydroxide, manganesecarbonate, manganese acetate, manganese nitrate, and the like andcombinations thereof. Preferably, the manganese oxide is in the form ofpowdered manganese oxide.

[0069] The aluminum-containing material will preferably be present inthe inventive composition in an amount in the range of from about 1.0 toabout 30 weight percent, preferably in an amount in the range of fromabout 5 to about 25 weight percent, and most preferably, in the range offrom 10 to 20 weight percent, based on the total weight of the inventivecomposition.

[0070] The silicon-containing material will preferably be present in theinventive w composition in an amount in the range of from about 10 toabout 40 weight percent silicon-containing material based on the totalweight of the inventive composition, more preferably in an amount in therange of from about 12 to about 30 weight percent, and most preferablyin the range of from 13 to 20 weight percent.

[0071] The inventive composition can be a particulate in the form of oneof granules, extrudates, tablets, spheres, pellets, or microspheres,preferably, the particulate is a microsphere.

[0072] In accordance with the present invention, the inventivecomposition(s) can be produced by the following inventive process.

[0073] In the production of an inventive composition, the compositioncan generally be prepared by admixing a liquid, manganese oxide, asilicon-containing material, alumina, and a promoter in appropriateproportions by any suitable method or manner which provides for theintimate mixing of such components to thereby provide a substantiallyhomogenous mixture thereof comprising a liquid, manganese oxide, asilicon-containing material, alumina, and a promoter. The term“admixing,” as used herein, denotes mixing components in any orderand/or any combination or sub-combination. Any suitable means foradmixing the components of the inventive composition can be used toachieve the desired dispersion of such components. Examples of suitableadmixing include, but are not limited to, mixing tumblers, stationaryshelves or troughs, Eurostar mixers, which are of the batch orcontinuous type, impact mixers, and the like. It is presently preferredto use a Eurostar mixer in the admixing of the components of theinventive composition.

[0074] The liquid can be any solvent capable of dispersing manganeseoxide, a silicon-containing material, alumina, and a promoter, and,preferably, the liquid can be selected from the group consisting ofwater, ethanol, acetone and combinations of any two or more thereof.Most preferably, the liquid is water.

[0075] The components of the inventive composition are mixed to providea mixture which can be in the form selected from the group consisting ofa wet mix, dough, paste, slurry and the like. Such mixture can then beshaped to form a particulate selected from the group consisting of agranule, an extrudate, a tablet, a sphere, a pellet, or a microsphere.For example, if the resulting mixture is in the form of a wet mix, thewet mix can be densified, dried under a drying condition as disclosedhereinafter, calcined under a calcining condition as disclosedhereinafter, and thereafter shaped, or particulated, through thegranulation of the densified, dried, calcined mix to form granulates.Also, for example, when the mixture of the components results in a formof the mixture which is either in a dough state, or a paste state, suchmixture can then be shaped, preferably extruded to form a particulate,more preferably a cylindrical extrudate having a diameter in the rangeof from about {fraction (1/32)} inch to about ½ inch, and any suitablelength, preferably a length in the range of from about ⅛ inch to about 1inch. The resulting particulates, preferably cylindrical extrudates, arethen dried under a drying condition as disclosed hereinafter and thencalcined under a calcining condition as disclosed hereinafter. Morepreferably, when the mix is in the form of a slurry, the particulationof such slurry is achieved by spray drying the slurry to formmicrospheres thereof having a size of about 500 or less microns. Suchmicrospheres are then subjected to drying under a drying condition asdisclosed hereinafter and are then calcined under a calcining conditionas disclosed hereinafter.

[0076] When the particulation is achieved by preferably spray drying, adispersant component can be utilized and can be any suitable compoundthat helps to promote the spray drying ability of the mix which ispreferably in the form of a slurry. In particular, these components areuseful in preventing deposition, precipitation, settling, agglomerating,adhering, and caking of solid particles in a fluid medium. Suitabledispersants include, but are not limited to, condensed phosphates,sulfonated polymers, and combinations thereof. The term “condensedphosphates” refers to any dehydrated phosphate where the H₂O:P₂O₅ isless than about 3:1. Specific examples of suitable dispersants includesodium pyrophosphate, sodium metaphosphate, sulfonated styrene maleicanhydride polymer, and combinations thereof. The amount of dispersantcomponent used is generally in the range of from about 0.01 weightpercent based on the total weight of the components to about 10 weightpercent. Preferably, the amount of the dispersant component used isgenerally in the range of from about 0.1 weight percent to about 8weight percent.

[0077] In preparing the preferred spray dried composition, an acidcomponent can be used. In general, the acid component can be an organicacid or a mineral acid such as nitric acid. If the acid component is anorganic acid, it is preferred to be a carboxylic acid. If the acidcomponent is a mineral acid, it is preferred to be a nitric acid or aphosphoric acid. Mixtures of these acids can also be used. Generally,the acid is used with water to form a dilute aqueous acid solution. Theamount of acid in the acid component is generally in the range of fromabout 0.01 volume percent based on the total volume of the acidcomponent to about 20 volume percent.

[0078] Generally, the spray dried material has a mean particle size inthe range of from about 10 micrometers to about 1000 micrometers,preferably in the range of from about 20 micrometers to from about 150micrometers.

[0079] The term “mean particle size” refers to the size of theparticulate material as determined by using a RO-TAP® Testing SieveShaker, manufactured by W. S. Tyler Inc., of Mentor, Ohio, or othercomparable sieves. The material to be measured is placed in the top of anest of standard 8-inch diameter stainless steel framed sieves with apan on the bottom. The material undergoes sifting for a period of about10 minutes; thereafter, the material retained on each sieve is weighed.The percent retained on each sieve is calculated by dividing the weightof the material retained on a particular sieve by the weight of theoriginal sample. This information is used to compute the mean particlesize.

[0080] The mixture is then dried to form a dried mixture. The dryingconditions, as referred to herein, can include a temperature in therange of from about 150° F. to about 450° F., preferably in the range offrom about 190° F. to about 410° F. and, most preferably, in the rangeof from 200° F. to 350° F. Such drying conditions can also include atime period generally in the range of from about 0.5 hour to about 60hours, preferably in the range of from about 1 hour to about 40 hours,and most preferably, in the range of from 1.5 hours to 20 hours. Suchdrying conditions can also include a pressure generally in the range offrom about atmospheric (i.e., about 14.7 pounds per square inchabsolute) to about 150 pounds per square inch absolute (psia),preferably in the range of from about atmospheric to about 100 psia and,most preferably about atmospheric, so long as the desired temperaturecan be maintained. Any drying method(s) known to one skilled in the artsuch as, for example, air drying, heat drying, and the like andcombinations thereof can be used. Preferably, heat drying is used.

[0081] The dried mixture is then calcined to form a calcined mixture.The calcining conditions, as referred to herein, can include atemperature in the range of from about 400° F. to about 1500° F.,preferably in the range of from about 800° F. to about 1500° F. and,more preferably, in the range of from 900° F. to 1400° F. Such calciningconditions can also include a pressure, generally in the range of fromabout 7 psia to about 750 psia, preferably in the range of from about 7psia to about 450 psia and, most preferably, in the range of from 7 psiato 150 psia, and a time period in the range of from about 1 hour toabout 60 hours, preferably for a time period in the range of from about1 hour to about 20 hours and, most preferably, for a time period in therange of from 1 hour to 15 hours. In the process of this invention, thecalcination can convert at least a portion of the alumina to aluminate.

[0082] The calcined mixture is thereafter subjected to reduction with asuitable reducing agent, preferably hydrogen or an appropriatehydrocarbon, so as to produce a composition having a substantiallyreduced valence promoter content therein, preferably a substantiallyzero-valent promoter content therein, with such zero-valent promoterbeing present in an amount sufficient to permit the removal of sulfurfrom a hydrocarbon stream such as cracked gasoline or diesel fuel,according to the process disclosed herein.

[0083] The reduction conditions can include a temperature in the rangeof from about 100° F. to about 1500° F., a pressure in the range of fromabout 15 psia to about 1500 psia and for a time sufficient to permit theformation of a reduced valence promoter.

[0084] The composition is then recovered.

[0085] In accordance with the present invention, the inventivecomposition(s) can also be produced by the following inventive process.

[0086] In the production of an inventive composition of the presentinvention, the composition can generally be prepared by admixing aliquid, manganese oxide, a silicon-containing material, and alumina inappropriate proportions by any suitable methods or manner which providesfor the intimate mixing of such components to thereby provide asubstantially homogenous mixture comprising a liquid (as describedabove), manganese oxide, a silicon-containing material, and alumina. Anysuitable means for admixing these components, as described above, can beused to achieve the desired dispersant of such components.

[0087] The components are mixed to provide a mixture which can be in theform selected from the group consisting of a wet mix, dough, paste,slurry, and the like. Such mixture can then optionally be shaped bydensifying, extruding, or spray drying to form a particulate selectedfrom the group consisting of a granule, an extrudate, a tablet, asphere, a pellet, or a microsphere, as described above.

[0088] The mixture is then dried to form a dried mixture, according tothe drying conditions described above.

[0089] The dried mixture is then calcined to form a calcined mixtureaccording to the calcining conditions described above. This calciningstep converts at least a portion of the alumina to aluminate.

[0090] The calcined mixture comprising manganese oxide, asilicon-containing material, and alumina (or aluminate), is thenincorporated with a promoter. The promoter can be incorporated into oronto the calcined mixture by any suitable means or method known in theart for incorporating a promoter into or onto a substrate material.

[0091] A preferred method of incorporating is to impregnate using anystandard incipient wetness impregnation technique (i.e. essentiallycompletely or partially filling the pores of a substrate material with asolution of the incorporating elements) for impregnating a substrate.This preferred method uses an impregnating solution comprising thedesirable concentration of a promoter so as to ultimately provide apromoted mixture that can then be subjected to drying and calciningfollowed by reduction with a reducing agent such as hydrogen.

[0092] A preferred impregnating solution comprises a solution formed bydissolving a metal containing compound, preferably such metal containingcompound is in the form of a metal salt such as a metal chloride, ametal nitrate, a metal sulfate, and the like and combinations thereof,in a solvent such as water, alcohols, esters, ethers, ketones, andcombinations thereof. The concentration of the metal promoter in thesolution can be in the range of from about 0.1 gram of metal promoterper gram of solution to about 5 grams of metal promoter per gram ofsolution. Preferably, the weight ratio of metal promoter to the solventof such solution can be in the range of from about 1:1 to about 4:1 but,more preferably it is in the range of from 1.5:1 to 3:1. It is preferredfor the particulates to be impregnated with a nickel component by use ofa solution containing nickel nitrate hexahydrate dissolved in water.

[0093] Following the incorporating of the calcined mixture, preferablyby impregnation, with a promoter, the resulting promoted mixture is thensubjected to drying under drying conditions, as described above, andcalcined under calcining conditions, as described above, to form acalcined promoted mixture. The calcined promoted mixture can then besubjected to reduction with a reducing agent, as described above, tothereby provide an inventive composition. The composition can then berecovered.

[0094] In preparing the spray dried composition, a promoter can be addedto the spray dried composition as a component of the original mixture,or it can be added after the original mixture has been spray dried andcalcined. If a promoter is added to the spray dried composition after ithas been spray dried and calcined, the spray dried composition should bedried and calcined a second time. The spray dried composition ispreferably dried a second time at a temperature generally in the rangeof from about 100° F. to about 650° F. Preferably, the spray-driedcomposition can be dried a second time at a temperature generally in therange of from about 150° F. to about 600° F. and, more preferably, inthe range of from 200° F. to 550° F. The time period for conducting thedrying the second time is generally in the range of from about 0.5 hourto about 8 hours, preferably in the range of from about 1 hour to about6 hours, and more preferably in the range of from 1.5 hours to 4 hours.Such drying a second time is generally carried out at a pressure in therange of from about atmospheric (i.e. about 14.7 psia) to about 100psia, preferably about atmospheric. This spray dried composition is thencalcined, preferably in an oxidizing atmosphere such as in the presenceof oxygen or air, under calcining conditions, as described above.

[0095] This invention also includes a novel process for the removal ofsulfur from a hydrocarbon stream. This process comprises:

[0096] a) contacting the hydrocarbon stream with a compositioncomprising manganese oxide and a promoter wherein at least a portion ofthe promoter is present as a reduced valence promoter in an amount whichwill effect the removal of sulfur from the hydrocarbon stream in adesulfurization zone under conditions such that there is formed adesulfurized hydrocarbon stream and a sulfurized composition;

[0097] b) separating the desulfurized hydrocarbon stream from thesulfurized composition thereby forming a separated desulfurizedhydrocarbon stream and a separated sulfurized composition;

[0098] c) regenerating at least a portion of the separated sulfurizedcomposition in a regeneration zone so as to remove at least a portion ofthe sulfur contained therein and/or thereon thereby forming aregenerated composition;

[0099] d) reducing the regenerated composition in an activation zone soas to provide a reduced composition having a reduced valence promotercontent therein which will effect the removal of sulfur from ahydrocarbon stream when contacted with same; and thereafter

[0100] e) returning at least a portion of the reduced composition to thedesulfurization zone.

[0101] In step (a), the composition can also comprise, consist of, orconsist essentially of manganese oxide, a silicon-containing material,an aluminum-containing material selected from the group consisting ofalumina, aluminate, and combinations thereof, an aluminate and apromoter wherein at least a portion of the promoter is present as areduced valence promoter in an amount which will effect the removal ofsulfur from the hydrocarbon stream in a desulfurization zone underconditions such that there is formed a desulfurized hydrocarbon streamand a sulfurized composition.

[0102] The contacting, in step a), of the hydrocarbon stream with theinventive composition in the desulfurization zone can be by any methodknown to those skilled in the art.

[0103] The desulfurization zone can be any zone wherein desulfurizationof a hydrocarbon stream can take place. Examples of suitable zones arefixed bed reactors, moving bed reactors, fluidized bed reactors,transport reactors, and the like. Presently a fluidized bed reactor or afixed bed reactor is preferred.

[0104] The desulfurization zone of step a) includes the followingconditions: total pressure, temperature, weight hourly space velocity,and hydrogen flow. These conditions are such that the inventivecomposition can desulfurize the hydrocarbon stream to produce adesulfurized hydrocarbon stream and a sulfurized composition.

[0105] The total pressure can be in the range of from about 15 poundsper square inch absolute (psia) to about 1500 psia. However, it ispresently preferred that the total pressure be in a range of from about50 psia to about 500 psia.

[0106] In general, the temperature should be sufficient to keep thehydrocarbon stream in essentially a vapor or gas phase. While suchtemperatures can be in the range of from about 100° F. to about 1000°F., it is presently preferred that the temperature be in the range offrom about 400° F. to about 800° F. when treating a cracked-gasoline,and in the range of from about 500° F. to about 900° F. when treating adiesel fuel.

[0107] Weight hourly space velocity (“WHSV”) is defined as the numericalratio of the rate at which a hydrocarbon stream is charged to thedesulfurization zone in pounds per hour at standard conditions attemperature and pressure (STP) divided by the pounds of compositioncontained in the desulfurization zone to which the hydrocarbon stream ischarged. In the practice of the present invention, such WHSV should bein the range of from about 0.5 hr.⁻¹ to about 50 hrs.⁻¹, preferably inthe range of from about 1 hr.⁻¹ to about 50 hrs.⁻¹.

[0108] Any suitable hydrocarbon stream, which comprises, consists of, orconsists essentially of sulfur containing hydrocarbons can be used asthe feed to be contacted with the inventive composition. The hydrocarbonstream preferably comprises, consists of, or consists essentially of afuel selected from the group consisting of a cracked gasoline, dieselfuel, and combinations thereof.

[0109] The amount of atomic sulfur, as sulfur in the hydrocarbon streamcan be in the range of from about 100 ppm atomic sulfur by weight of thehydrocarbon stream to about 50,000 ppm. When the hydrocarbon stream iscracked gasoline, the amount of atomic sulfur can be in the range offrom about 100 ppm atomic sulfur by weight of the cracked gasoline toabout 10,000 ppm sulfur by weight of the cracked gasoline. When thehydrocarbon stream is diesel fuel, the amount of atomic sulfur can be inthe range of from about 100 ppm atomic sulfur by weight of the dieselfuel to about 50,000 ppm sulfur by weight of the diesel fuel.

[0110] As used herein, “sulfur” used in conjunction with “ppmw sulfur”or the term “atomic sulfur”, denotes the amount of atomic sulfur (about32 atomic mass units) in the sulfur-containing fluid, not the atomicmass, or weight, of a sulfur compound, such as an organo-sulfurcompound.

[0111] The cracked gasoline or diesel fuel, suitable as a feed in aprocess of the present invention, is a composition that contains, inpart, olefins, aromatics, sulfur, paraffins and naphthenes.

[0112] The amount of olefins in cracked gasoline is generally in therange of from about 10 to about 35 weight percent olefins based on thetotal weight of the cracked gasoline. For diesel fuel there isessentially no olefin content.

[0113] The amount of aromatics in cracked gasoline is generally in therange of from about 20 to about 40 weight percent aromatics based on thetotal weight of the cracked gasoline. The amount of aromatics in dieselfuel is generally in the range of from about 10 to about 90 weightpercent aromatics based on the total weight of the diesel fuel.

[0114] In carrying out the desulfurization step of a process of thepresent invention, it is preferred that the hydrocarbon stream be in agas or vapor phase. However, in the practice of the present invention,it is not essential that such hydrocarbon stream be totally in a gas orvapor phase.

[0115] In carrying out the desulfurizing step, it is presently preferredthat an agent be employed which interferes with any possible chemical orphysical reacting of the olefinic or aromatic compounds in thehydrocarbon stream which is being treated with the inventivecomposition. Preferably such agent is hydrogen.

[0116] Hydrogen flow in the desulfurization zone is generally such thatthe mole ratio of hydrogen to the hydrocarbon stream is the range offrom about 0.1 to about 10, preferably in the range of from about 0.2 toabout 3.

[0117] If desired, during the desulfurization of the cracked gasoline ordiesel fuel, diluents such as methane, carbon dioxide, flue gas,nitrogen, and the like and combinations thereof can be used. Thus, it isnot essential to the practice of the present invention that a highpurity hydrogen be employed in achieving the desired desulfurization ofthe hydrocarbon stream such as, but not limited to, cracked gasoline ordiesel fuel.

[0118] It is presently preferred when utilizing a fluidized bed reactorsystem that a composition be used having a particle size in the range offrom about 10 micrometers to about 1000 micrometers. Preferably, suchcomposition should have a particle size in the range of from about 20micrometers to about 500 micrometers, and, more preferably, in the rangeof from 30 micrometers to 400 micrometers. When a fixed bed reactorsystem is employed for the practice of a desulfurization process of thepresent invention, the composition should generally have a particle sizein the range of about {fraction (1/32)} inch to about ½ inch diameter,preferably in the range of from about {fraction (1/32)} inch to about ¼inch diameter.

[0119] It is further presently preferred to use a composition having asurface area in the range of about 1 square meter per gram (m²/g) toabout 1000 square meters per gram of composition, preferably in therange of from about 1 m²/g to about 800 m²/g.

[0120] The desulfurized hydrocarbon stream can be separated from thesulfurized composition by any appropriate separation method known in theart thereby forming a separated desulfurized hydrocarbon stream and aseparated sulfurized composition.

[0121] Examples of such means are cyclonic devices, settling chambers,impingement devices for separating solids and gases, and the like andcombinations thereof. Separation can include, but is not limited to,allowing the hydrocarbon stream to flow out of the desulfurization zone.The desulfurized gaseous cracked gasoline or desulfurized gaseous dieselfuel, can then be recovered and preferably liquefied. Liquification ofsuch desulfurized hydrocarbon streams can be accomplished by any mannerknown in the art.

[0122] The amount of sulfur in the desulfurized hydrocarbon stream,following treatment in accordance with a desulfurization process of thepresent invention, is less than about 300 ppm sulfur by weight ofhydrocarbon stream, preferably less than about 150 ppm sulfur by weightof hydrocarbon stream, and more preferably less than about 50 ppm sulfurby weight of hydrocarbon stream.

[0123] In carrying out the process of the present invention, if desired,a stripper unit can be inserted before and/or after the regeneration ofthe sulfurized composition. Such stripper will serve to remove aportion, preferably all, of any hydrocarbon from the sulfurizedcomposition. Such stripper can also serve to remove oxygen and sulfurdioxide from the system prior to the introduction of the regeneratedcomposition into the activation zone (i.e., reduction zone). Thestripping comprises a set of conditions that include total pressure,temperature, and a stripping agent partial pressure.

[0124] Preferably, the total pressure in the stripper when employed isin the range of from about 25 psia to about 500 psia.

[0125] Temperature for such stripping can be in the range of from about100° F. to about 1000° F.

[0126] The stripping agent is a composition that helps to removehydrocarbon from the sulfurized composition. Preferably, the strippingagent is nitrogen. The sulfurized composition can have sulfur containedtherein (for example, within the pores of the composition) or thereon(for example, located on the surface of the composition).

[0127] The regeneration zone employs a set of conditions that includestotal pressure and sulfur removing agent partial pressure. The totalpressure is generally in the range of from about 25 psia to about 50psia.

[0128] The sulfur removing agent partial pressure is generally in therange of from about 1% to about 25% of the total pressure.

[0129] The sulfur-removing agent is a composition that helps to generategaseous sulfur containing compounds and oxygen containing compounds suchas sulfur dioxide, as well as to burn off any remaining hydrocarbondeposits that might be present. The preferred sulfur removing agentsuitable for use in the regeneration zone is selected from oxygencontaining gases such as, but not limited to, air.

[0130] The temperature in the regeneration zone is generally in therange of from about 100° F. to about 1500° F., preferably in the rangeof from about 800° F. to about 1200° F.

[0131] The regeneration zone can be any vessel wherein the desulfurizingor regeneration of the sulfurized composition can take place.

[0132] The regenerated composition is then reduced in an activation zonewith a reducing agent including, but not limited to, hydrogen, so thatat least a portion of the promoter content of the composition is reducedto produce a reduced composition having a reduced valence promotercontent to permit the removal of sulfur from the hydrocarbon streamaccording to the inventive process disclosed herein.

[0133] In general, when practicing the present invention, deactivation,i.e., reduction, of the desulfurized composition is carried out at atemperature in the range of from about 100° F. to about 1500° F. and ata pressure in the range of from about 15 psia to about 1500 psia. Suchreduction is carried out for a time sufficient to achieve the desiredlevel of promoter reduction of the promoter, which is preferablycontained in the skin of the composition. Such reduction can generallybe achieved in a time period in the range of from about 0.01 hour toabout 20 hours.

[0134] Following the activation, i.e., reduction, of the regeneratedcomposition, at least a portion of the resulting reduced composition canbe returned to the desulfurization zone.

[0135] In carrying out the process of the present invention, the stepsof desulfurization, regeneration, reduction, and optionally strippingbefore and/or after such regeneration can be accomplished in the singlezone or vessel or in multiple zones or vessels.

[0136] When carrying out the process of the present invention in a fixedbed reactor system, the steps of desulfurization, regeneration,reduction, and optionally stripping before and/or after suchregeneration are accomplished in a single zone or vessel.

[0137] The desulfurized cracked gasoline can be used in the formulationof gasoline blends to provide gasoline products suitable for commercialconsumption and can also be used where a cracked gasoline containing lowlevels of sulfur is desired.

[0138] The desulfurized diesel fuel can be used in the formulation ofdiesel fuel blends to provide diesel fuel products.

EXAMPLES

[0139] The following examples are intended to be illustrative of thepresent invention and to teach one of ordinary skill in the art to makeand use the invention. These examples are not intended to limit theinvention in any way.

Example I

[0140] A manganese/alumina/perlite composition promoted with cobalt wasprepared. 176 grams of cobalt nitrate hexahydrate were added to 242grams of deionized water and mixed in a Eurostar mixer. To thissolution, 25.5 grams of Condea Disperal alumina (an acid dispersibleboehmite alumina) were slowly added while mixing continued. 100.2 gramsof manganese oxide (Mn₂O₃) and 25.5 grams of perlite (Sibrico Sil-Kleer#27-M) were dry mixed and added to the solution of cobalt and alumina.After mixing thoroughly, the solution was put into a muffle furnace. Thetemperature was increased 3 degrees ° C. per minute to 150° C. and heldthere for an hour. The temperature was then increased to 635° C. andheld there for an hour. After cooling, the sample was crushed, sizedbetween 840 and 1700 microns, and then tested. Analysis of this sampleis given in Table V.

Example II

[0141] The cobalt composition as prepared in Example I was tested forits desulfurization ability as follows. 10 grams of the composition asprepared were placed in a ½ inch diameter quartz tube having a length ofabout 12 inches and having a glass frit positioned above the lowerone-third so as to provide an inert support for the bed of sorbent.

[0142] During each reaction cycle, the reactor was maintained at atemperature of 750° F. and a pressure of 15 pounds per square inchabsolute (psia). Hydrogen flow was at 130 standard cubic centimeters perminute (sccm) diluted with 130 sccm of nitrogen. Gaseouscracked-gasoline was pumped upwardly through the reactor at a rate of13.4 ml per hour. Such conditions are hereinafter referred to as“reaction conditions.”

[0143] The gaseous cracked-gasoline had a motor octane number of 80.5(MON) or 91.4 (RON) by engine tests, an olefin content of 20.4 weightpercent, 340 parts per million (ppm) sulfur by weight sulfur-compoundsbased on the total weight of the gaseous cracked-gasoline with about 95weight percent of the sulfur in the form of thiophenic compounds.

[0144] Before Cycle 1 was initiated, the composition was reduced withhydrogen flowing at a rate of 300 sccm at a temperature of 750° F. for aperiod of one hour. Such conditions are hereinafter referred to as“reducing conditions.” Each reaction cycle consisted of four hours withthe product sulfur (ppm) for each cycle measured after two, three, andfour hours of exposure to the feed.

[0145] After completion of the reaction cycle, the composition wasflushed with nitrogen at 750° F. for fifteen minutes. The temperaturewas then raised to 1000° F. where the composition was regenerated under100 sccm air and 200 sccm nitrogen for two hours. The temperature wasthen decreased to 750° F. and the sample purged with nitrogen for 15minutes. Such conditions are hereinafter referred to as “regenerationconditions.” Cycle 2 began, like Cycle 1 under reducing conditions;i.e., with treatment at 750° F. of the sorbent in hydrogen at a flowrate 300 sccm for one hour.

[0146] The composition in Example I was tested over three reactioncycles with regeneration occurring after Cycle 1 and Cycle 2. Theresults in Table I were obtained where the values given are the partsper million by weight of sulfur in the product after the second hour,third hour, and fourth hour of treatment, respectively. It should benoted that this composition showed greater than 90% desulfurizationactivity even after two regenerations of the composition. TABLE I TimeCycle 1 (ppm S) Cycle 2 (ppm S) Cycle 3 (ppm S) Second Hour 9 16 27Third Hour 10  19 32 Fourth Hour 6 19 35

[0147] Table VI summarizes the effect of the cobalt promoted manganesecomposition upon octane number change. The change in RON and MON iscalculated from gas chromatographic analysis of the feed and productsamples. The results clearly demonstrate that these cobalt promotedcompositions are expected to lead to very small octane changes even athigh desulfurization activity.

Example III

[0148] A manganese/alumina/perlite composition promoted with nickel wasprepared. 176.3 grams of nickel nitrate hexahydrate were added to 58grams of deionized water and mixed in a Eurostar mixer. To thissolution, 25.6 grams of Condea Disperal alumina (an acid dispersibleboehmite alumina) were slowly added while mixing continued. 100.0 gramsof manganese oxide (Mn₂O₃) and 25.5 grams of perlite (Sibrico Sil-Kleer#27-M) were dry mixed and added to the solution of nickel and alumina.After mixing thoroughly, the solution was put into a muffle furnace. Thetemperature was increased 3 degrees ° C. per minute to 150° C. and heldthere for an hour. The temperature was then increased to 635° C. andheld there for an hour. After cooling, the sample was crushed, sizedbetween 840 and 1700 microns, and then tested. Analysis of this sampleis given in Table V.

Example IV

[0149] 10 grams of the composition as prepared in Example III weretested for desulfurization activity as described in Example II. Thecomposition was tested over three reaction cycles with the results inTable II given in parts per million by weight of sulfur in the productafter the second hour, third hour, and fourth hour of treatment,respectively. It should be noted that the nickel promoted compositiondemonstrates exceptionally high desulfurization activity, especiallyduring the first reaction cycle. TABLE II Time Cycle 1 (ppm S) Cycle 2(ppm S) Cycle 3 (ppm S) Second Hour <1 11 15 Third Hour <1 19 39 FourthHour <1 31 57

[0150] Table VI summarizes the effect of the nickel promoted manganesecomposition upon octane number change. The change in RON and MON iscalculated from gas chromatographic analysis of the feed and productsamples. The data demonstrate that small octane changes are expectedeven at high desulfurization activity over these nickel promotedcompositions.

Example V

[0151] A manganese/alumina/perlite composition promoted with nominal(90/10) weight ratio of nickel and zinc was prepared. First, a nickeloxide and zinc oxide mixture was prepared by dissolving 453 grams ofnickel nitrate hexahydrate and 47 grams of zinc nitrate hexahydrate indistilled water. This was then blended with a solution containing 200grams ammonium carbonate in a Eurostar mixer. A nickel/zinc/oxideprecipitate was then formed which was filtered through a Buchner funneland dried overnight in a muffle furnace at 635° C. To prepare thecomposition, 15.0 grams of Vista Dispal alumina was blended with waterin a Eurostar mixer. 50.2 grams of manganese oxide (Mn₂O₃), 27.5 gramsof the nickel/zinc mixture, and 15.0 grams of perlite (SilbricoSil-Kleer #27-M) were dry mixed and added to the alumina. After mixingthoroughly, the solution was put into a muffle furnace and driedovernight at 635° C. After cooling, the sample was crushed, sizedbetween 840 and 1700 microns, and then tested. The elemental analysis isgiven in Table V.

Example VI

[0152] 10 grams of the composition as prepared in Example V were testedfor desulfurization activity as described in Example II. The compositionwas tested over three reaction cycles with the results in Table IIIgiven in parts per million by weight of sulfur in the product after thesecond hour, third hour, and fourth hour of treatment, respectively. Theamount of sulfur removed was in the range of from about 39% to about89%. TABLE III Time Cycle 1 (ppm 5) Cycle 2 (ppm S) Cycle 3 (ppm S)Second Hour 37  73  89 Third Hour 72 144 177 Fourth Hour 138  206 194

[0153] Table VI summarizes the effect of the 90/10 nickel/zinc promotedmanganese composition upon octane number change. The change in RON andMON average is calculated from gas chromatographic analysis of the feedand product samples. The data demonstrate that small octane changes areexpected even when 75% of the feed sulfur is removed over these 90/10nickel/zinc promoted compositions.

Example VII

[0154] A manganese/alumina/perlite composition promoted with nominal(70/30) weight ratio of nickel and zinc was prepared. First, a nickeloxide and zinc oxide mixture was prepared. 720 grams of nickel nitratehexahydrate and 290 grams of zinc nitrate hexahydrate were dissolved indistilled water. This was then blended with a solution of 390 grams ofammonium carbonate in a Eurostar mixer. A nickel/zinc/oxide precipitatewas then formed which was filtered through a Buchner funnel and driedovernight in a muffle furnace at 635° C. To prepare the composition,18.1 grams of Vista Dispal alumina was blended with water in a Eurostarmixer. 50.5 grams of manganese oxide (Mn₂O₃), 42.3 grams of thenickel/zinc mixture, and 18.0 grams of perlite (Silbrico Sil-Kleer#27-M) were dry mixed and added to the alumina. After mixing thoroughly,the solution was put into a muffle furnace and dried overnight at 635°C. After cooling, the sample was crushed, sized between 840 and 1700microns, and then tested. The elemental analysis is given in Table V.

Example VIII

[0155] 10 grams of the composition as prepared in Example VII weretested for desulfurization activity as described in Example II. Thecomposition was tested over three reaction cycles with the results inTable IV given in parts per million by weight of sulfur in the productafter the second hour, third hour, and fourth hour of treatment,respectively. The amount of sulfur removed was in the range of fromabout 67% to about 97%. TABLE IV Time Cycle 1 (ppm S) Cycle 2 (ppm S)Cycle 3 (ppm S) Second Hour  9 24 61 Third Hour 16 64 96 Fourth Hour 31101  112 

[0156] Table VI summarizes the effect of the 70/30 nickel/zinc promotedmanganese composition upon octane number change. The change in RON andMON average is calculated from gas chromatographic analysis of the feedand product samples. The data demonstrate that small octane changes areexpected even at high desulfurization activity over these 70/30nickel/zinc promoted compositions. TABLE V Elemental Analyses ofCompositions (Wt %) by X-ray Fluorescence Element Example I Example IIIExample V Example VII Silicon 7.2 7.3 7.8 6.7 Aluminum 8.1 6.6 12.8 10.3Manganese 35.1 37.6 33.3 26.7 Cobalt 14.5 — — — Nickel — 16.3 9.4 16.6Zinc — — 1.5 7.7

[0157] TABLE VI Change in Octane Number and Percent Sulfur Removed forManganese Oxide Compositions for Product Taken After Third Hour PercentSulfur Example Cycle Promoter Removed Octane Change* II 1 Cobalt 97.1−0.24 II 2 Cobalt 94.5 +0.08 IV 2 Nickel 94.5 −0.12 VI 1 90/10Nickel/Zinc 78.9 +0.08 VIII 1 70/30 Nickel/Zinc 95.3 −0.05

That which is claimed:
 1. A composition comprising: (a) manganese oxide; and (b) a promoter wherein at least a portion of said promoter is present as a reduced valence promoter.
 2. A composition in accordance with claim 1 wherein said promoter is present in an amount which will effect the removal of sulfur from a hydrocarbon stream when contacted with said composition under desulfurization conditions.
 3. A composition in accordance with claim 1 wherein said promoter comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, and combinations of any two or more thereof.
 4. A composition in accordance with claim 1 wherein said manganese oxide is present in an amount in the range of from about 10 to about 90 weight percent.
 5. A composition in accordance with claim 1 wherein said manganese oxide is present in an amount in the range of from about 40 to about 80 weight percent.
 6. A composition in accordance with claim 1 wherein said manganese oxide is present in an amount in the range of from 50 to 70 weight percent.
 7. A composition in accordance with claim 1 wherein said promoter is present in an amount in the range of from about 1 to about 60 weight percent.
 8. A composition in accordance with claim 1 wherein said promoter is present in an amount in the range of from about 5 to about 40 weight percent.
 9. A composition in accordance with claim 1 wherein said promoter is present in an amount in the range of from 8 to 20 weight percent.
 10. A composition in accordance with claim 1 wherein said promoter comprises nickel.
 11. A composition in accordance with claim 1 wherein said promoter comprises cobalt.
 12. A composition in accordance with claim 1 wherein said promoter comprises a solid solution of nickel and zinc.
 13. A composition in accordance with claim 1 wherein said composition is a particulate in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres.
 14. A composition in accordance with claim 13 wherein said particulate is a microsphere.
 15. A composition comprising: (a) manganese oxide; (b) a silicon-containing material; (c) an aluminum-containing material selected from the group consisting of alumina, aluminate, and combinations thereof; and (d) a promoter wherein at least a portion of said promoter is present as a reduced valence promoter.
 16. A composition in accordance with claim 15 wherein said promoter is present in an amount which will effect the removal of sulfur from a hydrocarbon stream when contacted with said composition under desulfurization conditions.
 17. A composition in accordance with claim 15 wherein said promoter comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, and combinations of any two or more thereof.
 18. A composition in accordance with claim 15 wherein said manganese oxide is present in an amount in the range of from about 10 to about 90 weight percent.
 19. A composition in accordance with claim 15 wherein said manganese oxide is present in an amount in the range of from about 40 to about 80 weight percent.
 20. A composition in accordance with claim 15 wherein said manganese oxide is present in an amount in the range of from 50 to 70 weight percent.
 21. A composition in accordance with claim 15 wherein said promoter is present in an amount in the range of from about 1 to about 60 weight percent.
 22. A composition in accordance with claim 15 wherein said promoter is present in an amount in the range of from about 5 to about 40 weight percent.
 23. A composition in accordance with claim 15 wherein said promoter is present in an amount in the range of from 8 to 20 weight percent.
 24. A composition in accordance with claim 15 wherein said silicon-containing material is present in an amount in the range of from about 10 to about 40 weight percent and said aluminum-containing material is present in an amount in the range of from about 1 to about 30 weight percent.
 25. A composition in accordance with claim 15 wherein said silicon-containing material is present in an amount in the range of from about 12 to about 30 weight percent and said aluminum-containing material is present in an amount in the range of from about 5 to about 25 weight percent.
 26. A composition in accordance with claim 15 wherein said silicon-containing material is present in an amount in the range of from 13 to 20 weight percent and said aluminum-containing material is present in an amount in the range of from 10 to 20 weight percent.
 27. A composition in accordance with claim 15 wherein said promoter comprises nickel.
 28. A composition in accordance with claim 15 wherein said promoter comprises cobalt.
 29. A composition in accordance with claim 15 wherein said promoter comprises a solid solution of nickel and zinc.
 30. A composition in accordance with claim 15 wherein said silicon-containing material is present in the form of expanded perlite.
 31. A composition in accordance with claim 30 wherein said expanded perlite is milled.
 32. A composition in accordance with claim 15 wherein said composition is a particulate in the form of one of granules, extrudates, tablets, spheres, pellets, or miscrospheres.
 33. A composition in accordance with claim 32 wherein said particulate is a microsphere.
 34. A process for the production of a composition comprising: (a) admixing: 1) a liquid, 2) manganese oxide, 3) a silicon-containing material, 4) alumina, and 5) a promoter so as to form a mixture thereof; (b) drying said mixture so as to form a dried mixture; (c) calcining said dried mixture so as to form a calcined mixture; (d) reducing said calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein, and (e) recovering said composition.
 35. A process in accordance with claim 34 wherein said calcined mixture is reduced in step (d) such that said composition will effect the removal of sulfur from a stream of hydrocarbons when such stream is contacted with same under desulfurization conditions.
 36. A process in accordance with claim 34 wherein said promoter comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, and combinations of any two or more thereof.
 37. A process in accordance with claim 34 wherein said silicon-containing material is in the form of expanded perlite.
 38. A process in accordance with claim 34 wherein said mixture from step (a) is in the form of one of a wet mix, dough, paste, or slurry.
 39. A process in accordance with claim 34 wherein said mixture from step (a) is particulated prior to said drying in step (b).
 40. A process in accordance with claim 34 wherein said mixture from step (a) is particulated in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres prior to said drying in step (b).
 41. A process in accordance with claim 34 wherein said mixture from step (a) is particulated by spray drying in step (b) so as to form said dried mixture.
 42. A process in accordance with claim 34 wherein said mixture is dried in step (b) at a temperature in the range of from about 150° F. to about 450° F.
 43. A process in accordance with claim 34 wherein said dried mixture is calcined in step (c) at a temperature in the range of from about 400 to about 1500° F.
 44. A process in accordance with claim 34 wherein said manganese oxide is present in an amount in the range of from about 10 to about 90 weight percent.
 45. A process in accordance with claim 34 wherein said manganese oxide is present in an amount in the range of from about 40 to about 80 weight percent.
 46. A process in accordance with claim 34 wherein said manganese oxide is present in an amount in the range of from 50 to 70 weight percent.
 47. A process in accordance with claim 34 wherein said promoter is present in an amount in the range of from about 1 to about 60 weight percent.
 48. A process in accordance with claim 34 wherein said promoter is present in an amount in the range of from about 5 to about 40 weight percent.
 49. A process in accordance with claim 34 wherein said promoter is present in an amount in the range of from 8 to 20 weight percent.
 50. A process in accordance with claim 34 wherein said silicon-containing material is present in an amount in the range of from about 10 to about 40 weight percent and said alumina is present in an amount in the range of from about 1 to about 30 weight percent.
 51. A process in accordance with claim 34 wherein said silicon-containing material is present in an amount in the range of from about 12 to about 30 weight percent and said alumina is present in an amount in the range of from about 5 to about 25 weight percent.
 52. A process in accordance with claim 34 wherein said silicon-containing material is present in an amount in the range of from 13 to 20 weight percent and said alumina is present in an amount in the range of from 10 to 20 weight percent.
 53. A process in accordance with claim 34 wherein said promoter is comprised of nickel.
 54. A process in accordance with claim 34 wherein said promoter is comprised of cobalt.
 55. A process in accordance with claim 34 wherein said promoter is comprised of a solid solution of nickel and zinc.
 56. A process in accordance with claim 34 wherein said calcined mixture is reduced in step (d) at a temperature in the range of from about 100° F. to about 1500° F. and at a pressure in the range of from about 15 to about 1500 psia and for a time sufficient to permit the formation of a reduced valence promoter.
 57. A process in accordance with claim 34 wherein said dried mixture is calcined in step (c) to convert at least a portion of said alumina to aluminate.
 58. A composition prepared by the process of claim
 34. 59. A composition prepared by the process of claim
 39. 60. A composition prepared by the process of claim
 44. 61. A composition prepared by the process of claim
 45. 62. A composition prepared by the process of claim
 47. 63. A composition prepared by the process of claim
 48. 64. A composition prepared by the process of claim
 50. 65. A process for the production of a composition comprising: (a) admixing: 1) a liquid, 2) manganese oxide, 3) a silicon-containing material, and 4) alumina so as to form a mixture thereof; (b) drying said mixture so as to form a dried mixture; (c) calcining said dried mixture so as to form a calcined mixture; (d) incorporating a promoter onto or into said calcined mixture so as to form a promoted mixture; (e) drying said promoted mixture so as to form a dried promoted mixture; (f) calcining said dried promoted mixture so as to form a calcined promoted mixture; (g) reducing said calcined promoted mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein; and (h) recovering said composition.
 66. A process in accordance with claim 65 wherein said calcined promoted mixture is reduced in step (g) such that said composition of step (g) will effect the removal of sulfur from a stream of hydrocarbons when such stream is contacted with same under desulfurization conditions.
 67. A process in accordance with claim 65 wherein said calcined mixture from step (c) is incorporated with a promoter comprised of at least one metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, and combinations of any two or more thereof.
 68. A process in accordance with claim 65 wherein said silicon-containing material is present in the form of expanded perlite.
 69. A process in accordance with claim 65 wherein said mixture from step (a) is in the form of one of a wet mix, dough, paste, or slurry.
 70. A process in accordance with claim 65 wherein said mixture from step (a) is particulated prior to drying in step (b).
 71. A process in accordance with claim 65 wherein said mixture from step (a) is particulated in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres.
 72. A process in accordance with claim 65 wherein said mixture from step (a) is particulated by spray drying in step (b) so as to form said dried mixture.
 73. A process in accordance with claim 65 wherein said mixture and said promoted mixture are dried in steps (b) and (e), respectively, at a temperature in the range of about 150° F. to about 450° F.
 74. A process in accordance with claim 65 wherein said dried mixture and said dried promoted mixture are calcined in steps (c) and (f), respectively, at a temperature in the range of about 400 to about 1500° F.
 75. A process in accordance with claim 65 wherein said manganese oxide is present in an amount in the range of from about 10 to about 90 weight percent.
 76. A process in accordance with claim 65 wherein said manganese oxide is present in an amount in the range of from about 40 to about 80 weight percent.
 77. A process in accordance with claim 65 wherein said manganese oxide is present in an amount in the range of from about 50 to about 70 weight percent.
 78. A process in accordance with claim 65 wherein said promoter is present in an amount in the range of from about 1 to about 60 weight percent.
 79. A process in accordance with claim 65 wherein and said promoter is present in an amount in the range of from about 5 to about 40 weight percent.
 80. A process in accordance with claim 65 wherein said promoter is present in an amount in the range of from 8 to 20 weight percent.
 81. A process in accordance with claim 65 wherein said silicon-containing material is present in an amount in the range of from about 10 to about 40 weight percent and said alumina is present in an amount in the range of from about 1.0 to about 30 weight percent.
 82. A process in accordance with claim 65 wherein said silicon-containing material is present in an amount in the range of from about 12 to about 30 weight percent and said alumina is present in an amount in the range of from about 5 to about 25 weight percent.
 83. A process in accordance with claim 65 wherein said silicon-containing material is present in an amount in the range of from 13 to 20 weight percent and said alumina is present in an amount in the range of from 10 to 20 weight percent.
 84. A process in accordance with claim 65 wherein said promoter is comprised of nickel.
 85. A process in accordance with claim 65 wherein said promoter is comprised of cobalt.
 86. A process in accordance with claim 65 wherein said promoter is comprised of a solid solution of nickel and zinc.
 87. A process in accordance with claim 65 wherein the reduction of said calcined promoted mixture in step (g) is carried out at a temperature in the range of from about 100° F. to about 1500° F. and at a pressure in the range of from about 15 to about 1500 psia and for a time sufficient to permit the formation of a reduced valence promoter.
 88. A process in accordance with claim 65 wherein said dried mixture from step (b) is calcined in step (c) to convert at least a portion of said alumina to aluminate.
 89. A composition prepared by the process of claim
 65. 90. A composition prepared by the process of claim
 70. 91. A composition prepared by the process of claim
 75. 92. A composition prepared by the process of claim
 76. 93. A composition prepared by the process of claim
 78. 94. A composition prepared by the process of claim
 79. 95. A composition prepared by the process of claim
 81. 96. A process for the removal of sulfur from a hydrocarbon stream comprising: (a) contacting said hydrocarbon stream with a composition comprising manganese oxide and a promoter wherein at least a portion of said promoter is present as a reduced valence promoter and in an amount which will effect the removal of sulfur from said hydrocarbon stream in a desulfurization zone under conditions such that there is formed a desulfurized hydrocarbon stream and a sulfurized composition; (b) separating said desulfurized hydrocarbon stream from said sulfurized composition thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition; (c) regenerating at least a portion of said separated sulfurized composition in a regeneration zone so as to remove at least a portion of the sulfur contained therein W and/or thereon thereby forming a regenerated composition; (d) reducing said regenerated composition in an activation zone so as to provide a reduced composition having a reduced valence promoter content therein which will effect the removal of sulfur from a hydrocarbon stream when contacted with same; and thereafter (e) returning at least a portion of said reduced composition to said desulfurization zone.
 97. A process in accordance with claim 96 wherein said hydrocarbon stream comprises a fuel selected from the group consisting of cracked-gasoline, diesel fuel, and combinations thereof.
 98. A process in accordance with claim 96 wherein said desulfurization in step (a) is carried out at a temperature in the range of from about 100° F. to about 1000° F. and a pressure in the range of from about 15 to about 1500 psia for a time sufficient to effect the removal of sulfur from said stream.
 99. A process in accordance with claim 96 wherein said regeneration in step (c) is carried out at a temperature in the range of from about 100° F. to about 1500° F. and a pressure in the range of from about 10 to about 1500 psia for a time sufficient to effect the removal of at least a portion of the sulfur from said separated sulfurized composition.
 100. A process in accordance with claim 96 wherein there is employed air in step (c) as a regeneration agent in said regeneration zone.
 101. A process in accordance with claim 96 wherein said regenerated composition from step (c) is subjected to reduction with hydrogen in step (d) in a hydrogenation zone which is maintained at a temperature in the range of from about 100° F. to about 1500° F. and at a pressure in the range of from about 15 to about 1500 psia and for a period of time sufficient to effect a reduction of the valence of the promoter content of said regenerated composition.
 102. A process in accordance with claim 96 wherein said separated sulfurized composition from step (b) is stripped prior to introduction into said regeneration zone in step (c).
 103. A process in accordance with claim 96 wherein said regenerated composition from step (c) is stripped prior to introduction to said activation zone in step (d).
 104. The cracked-gasoline product of the process of claim
 96. 105. The diesel fuel product of the process of claim
 96. 106. A process for the removal of sulfur from a hydrocarbon stream comprising: (a) contacting said hydrocarbon stream with a composition comprising manganese oxide, a silicon-containing material, an aluminum-containing material selected from the group consisting of alumina, aluminate, and combinations thereof, and a promoter wherein at least a portion of said promoter is present as a reduced valence promoter and in an amount which will effect the removal of sulfur from said hydrocarbon stream in a desulfurization zone under conditions such that there is formed a desulfurized hydrocarbon stream and a sulfurized composition; (b) separating said desulfurized hydrocarbon stream from said sulfurized composition thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition; (c) regenerating at least a portion of said separated sulfurized composition in a regeneration zone so as to remove at least a portion of the sulfur contained therein and/or thereon thereby forming a regenerated composition; (d) reducing said regenerated composition in an activation zone so as to provide a reduced composition having a reduced valence promoter content therein which will effect the removal of sulfur from a hydrocarbon stream when contacted with same; and thereafter (e) returning at least a portion of said reduced composition to said desulfurization zone.
 107. A process in accordance with claim 106 wherein said hydrocarbon stream comprises a fuel selected from the group consisting of cracked-gasoline, diesel fuel, and combinations thereof.
 108. A process in accordance with claim 106 wherein said desulfurization in step (a) is carried out at a temperature in the range of from about 100° F. to about 1000° F. and a pressure in the range of from about 15 to about 1500 psia for a time sufficient to effect the removal of sulfur from said stream.
 109. A process in accordance with claim 106 wherein said regeneration in step (c) is carried out at a temperature in the range of from about 100° F. to about 1500° F. and a pressure in the range of from about 10 to about 1500 psia for a time sufficient to effect the removal of at least a portion of the sulfur from said separated sulfurized composition.
 110. A process in accordance with claim 106 wherein there is employed air in step (c) as a regeneration agent in said regeneration zone.
 111. A process in accordance with claim 106 wherein said regenerated composition from step (c) is subjected to reduction with hydrogen in step (d) in a hydrogenation zone which is maintained at a temperature in the range of from about 100° F. to about 1500° F. and at a pressure in the range of from about 15 to about 1500 psia and for a period of time sufficient to effect a reduction of the valence of the promoter content of said regenerated composition.
 112. A process in accordance with claim 106 wherein said separated sulfurized composition from step (b) is stripped prior to introduction into said regeneration zone in step (c).
 113. A process in accordance with claim 106 wherein said regenerated composition from step (c) is stripped prior to introduction to said activation zone in step (d).
 114. The cracked-gasoline product of the process of claim
 106. 115. The diesel fuel product of the process of claim
 106. 